CN107189357A - A kind of epoxy-resin systems and preparation method thereof - Google Patents
A kind of epoxy-resin systems and preparation method thereof Download PDFInfo
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- CN107189357A CN107189357A CN201710561789.1A CN201710561789A CN107189357A CN 107189357 A CN107189357 A CN 107189357A CN 201710561789 A CN201710561789 A CN 201710561789A CN 107189357 A CN107189357 A CN 107189357A
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- epoxy
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/136—Phenols containing halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
Abstract
The invention discloses a kind of epoxy-resin systems, including following component by weight:100 parts of epoxy resin, 10 70 parts of curing agent, 1 20 parts of accelerator, 0.1 10 parts of covering.Viscosity B coefficent amount after a kind of epoxy-resin systems obtained by the present invention are placed 1 hour under 50 DEG C, 1bar is respectively less than 150%;50 DEG C, the hardening time under 50bar be 10 30 seconds.
Description
Technical field
The present invention relates to chemical material technical field, more particularly to a kind of epoxy-resin systems and preparation method thereof.
Background technology
Epoxy resin since the advent of the world is wide due to its excellent physical and chemical properties, and easy moulding process
Industry-by-industry is applied to generally, as the thermosetting resin that current industrial quarters is most widely used, property is optimal.Recently as wind
The industries such as power generating, automobile, Aero-Space are developed rapidly, and the status of reinforcing fiber/epoxy resin composite material becomes more and more important.
Fibre reinforced epoxy resin composite large-scale at present uses vacuum assisted resin transfer molding mostly
(VARTM), resin transfer moulding (RTM), the manufacture of reaction injection molded (RIM) technique, wherein RTM techniques because of closed moulding, into
The type cycle is shorter, and the advantages of production environment is good receives favor.But the problem of RTM technique generally existings following two aspects:(1) set
Fat is not ideal enough to the dipping of fiber.Common RTM is non-pressurized, only by gravity or is vacuumized, and liquid resin is immersed fiber
The amount of layer is limited, causes molding time long, and product voidage is high;(2) in large scale or baroque mould, resin flows not
It is balanced, it is impossible to be predicted and control.Limit application of the technique in terms of complex structural member shaping.Therefore will be by increasing
Press to accelerate the speed that resin immerses fibrous material, overcome above mentioned problem.Patent CN102675827 puts forward one kind and uses high pressure
The epoxy resin base carbon fiber composite material that resin transfer moulding quick shaping process (HP-ATM) makes.
In order to adapt to the requirement of high-pressure resin transfer modling quick shaping process, resin needs rapid curing.But in raw material
It is curable aliphatic amine especially in room temperature or slightly above room temperature, it is necessary to make stable resin in the set-up procedures such as mixing
Curative systems, it is difficult to accomplish both to ensure that the times such as raw material mixing are abundant, again can in shaping high speed curable;If addition
Suitable accelerator, can improve its solidification rate, but solidification rate can cause very much the time that can be used for raw material to mix too soon
It is short.
So, it is general to use on-line mixing technique in high-pressure resin transfer modling technique, i.e., by epoxy resin and curing agent
Metering is injected into mixing chamber respectively, after being mixed in mixing chamber, high pressure injection die cavity.This technique needs accurate control asphalt mixtures modified by epoxy resin
The flow velocity of fat and curing agent, installation cost is higher;Even with accurate current velocity controller, when the addition of curing agent is less
When, typically it also is difficult to accurately control flow velocity, causes epoxy resin/curing agent proportioning deviation occur with design load, influence product
Quality;Finally, the mixing of short time causes mixing uneven, can also influence product quality.
The content of the invention
The technical problem existed based on background technology, it is curable in room temperature or slightly above room temperature that the present invention, which is provided a kind of,
Epoxy-resin systems, its long-time stable at ambient pressure, and rapid curing under high pressure.So as to which raw material can be pre- at ambient pressure
First mix, it is not necessary to on-line mixing, that is, reduce manufacturing cost, be conducive to the raising of product quality.
The present invention proposes a kind of epoxy-resin systems, including following component by weight:It is 100 parts of epoxy resin, solid
10-70 parts of agent, 1-20 parts of accelerator, 0.1-10 parts of covering.
Described epoxy-resin systems, under 1bar pressure, more than 90% (weight ratio) of accelerator is dispersed in cladding
In agent phase.Described epoxy-resin systems, can also contain one kind in diluent, defoamer, coupling agent, antioxidant or many
Kind.
The epoxy resin is bisphenol A type epoxy resin, bisphenol f type epoxy resin, para-aminophenol epoxy resin, adjacent first
One kind in phenol-type epoxy resin, phenol aldehyde type epoxy resin, multiple functionality epoxide resin, preferably bisphenol A type epoxy resin.
It is preferred that, described curing agent includes one kind in aliphatic polybasic amine curing agent.
It is preferred that, described accelerator is one kind in phenol or derivative.
It is preferred that, described covering elects poly-succinic glyceride or polyadipate glyceride as.
It is preferred that, the covering is dispersed in asphalt mixtures modified by epoxy resin lipid phase with disperse phase, the covering dispersed phase it is flat
It is a diameter of less than 100 microns.
It is preferred that, the covering is uncrosslinked, and number-average molecular weight is 5000~25000g/mol.
A kind of preparation method of epoxy-resin systems, method and step is as follows:S1:Accelerator and covering are well mixed
Afterwards, cool down.S2:Mixture obtained by S1 is crushed to a diameter of less than 100 microns of particle using pulverizer;S3:By S2
Obtained particle is mixed with epoxy resin and curing agent, produces epoxy-resin systems.
Further, the mixing temperature of the S1 is 80-100 DEG C, and the mixing temperature of the S3 is 20-30 DEG C.
A kind of epoxy-resin systems proposed by the present invention are applied to prepare fibre enhancement epoxy composite material, and method and step is such as
Under:1) fiber cloth prefabricated component is put into mold cavity;2) close up mould, vacuumized by vavuum pump, will be produced by the present invention
Epoxy-resin systems inject die cavity by 30-80bar high pressure, then, are molded epoxy resin cure under high pressure.Described
Fiber cloth is the one or more in glass fabric, carbon cloth etc., preferably carbon cloth.
Compared with prior art, the device have the advantages that being:
1st, epoxy-resin systems of the invention at normal temperatures and pressures, due to being coated accelerator by covering, so promoting
Entering agent will not play a part of accelerating epoxy resin cure, and feedstock property is stable, the raw material in system can be enable to be sufficiently mixed,
Long term storage;Viscosity B coefficent amount after the epoxy-resin systems of the present invention are placed 1 hour under 50 DEG C, 1bar is respectively less than 150%;
2nd, when epoxy-resin systems of the invention apply to high-pressure resin transfer modling quick shaping process, in condition of high voltage
Under, covering rupture, the Epoxy curing accelerators being coated in covering are released, and accelerate the solidification rate of epoxy resin,
Reach quick-setting effect;Hardening time of the epoxy-resin systems of the present invention under 50 DEG C, 50bar is 10-30 seconds.
3rd, when epoxy-resin systems of the invention apply to high-pressure resin transfer modling quick shaping process, it is not necessary to online
Mixing, equipment manufacturing cost reduction, is conducive to the popularization of high-pressure resin transfer modling quick shaping process.
Embodiment
The present invention proposes a kind of epoxy-resin systems, and the present invention is made with reference to specific embodiment further to explain.
Detection project and its method of testing in embodiment:
1st, viscosity B coefficent (%):It is sufficiently mixed using blender after raw material, using rotation viscometer, tests 50 DEG C, 1bar
The initial viscosity of lower sample.Afterwards, at 50 DEG C, placed 1 hour under 1bar, rotation viscometer tested viscosity is used again, as the following formula
Calculate the viscosity B coefficent of sample in placement process:
Sample viscosity/initial viscosity × 100% after viscosity B coefficent (%)=1 hour
2nd, hardening time:DSC204HP type high-pressure type differential scanning calorimeters are produced using a Netzsch company to be surveyed
Examination.Under 1bar or 50bar, risen to 10 DEG C/min programming rate after 50 DEG C, be calculated as time zero, the isothermal of test sample
Cure profile.Using twice as 50 DEG C, 50bar lower hardening times of the time to peak for solidifying peak.
3rd, number-average molecular weight:Using chloroform as mobile phase, determined with exclusion chromatography (GPC).
4th, particle size:Sample size is measured using light scattering method.Using the equal average value of the number of diameter being averaged as sample
Diameter.
Raw material used in embodiment and comparative example:
Epoxy resin:Bisphenol A type epoxy resin;
Curing agent:G1:Diethylenetriamine;G2:Meng's alkane diamines.
Accelerator:C1:Phenol;C2:P-Chlorophenic acid.
Covering:B1:Poly-succinic glyceride, is prepared by the following method:Equimolar succinic acid and glycerine are protected in nitrogen
Under, in 160 DEG C of dehydrating polycondensation certain times, water white transparency solid is obtained after cooling.Prepare respectively number-average molecular weight for 5000,
10000th, 15000,20000,25000g/mol sample.(number-average molecular weight error is less than ± 10%.)
B2:Polyadipate glyceride, is prepared by the following method:By equimolar adipic acid and glycerine under nitrogen protection, in 160
DEG C dehydrating polycondensation certain time, water white transparency solid is obtained after cooling.Prepare respectively number-average molecular weight for 5000,10000,
15000th, 20000,25000g/mol sample.(number-average molecular weight error is less than ± 10%.)
Comparative example 1-4
By the proportioning of table 1, with an agitator, after 25 DEG C are well mixed epoxy resin, curing agent, accelerator, obtain
To epoxy-resin systems.Wherein, comparative example 1,2 is without using accelerator.
Tested viscosity change (50 DEG C, 1bar is placed 1 hour), hardening time (50 DEG C, 50bar), as a result it is listed in table 1.
Table 1
Conclusion:The epoxy systems of comparative example 1 and 2, although its viscosity B coefficent under the conditions of 50 DEG C, 1bar is very slow, but its
50 DEG C, curing rate is too slow under the conditions of 50bar, is not suitable for high-pressure resin transfer modling quick shaping process.Comparative example 3 and 4
Viscosity B coefficent is too fast under the conditions of 50 DEG C, 1bar, it is impossible to be pre-mixed.
Embodiment 1-8
By the proportioning of table 2, with an agitator, after 80 DEG C are well mixed accelerator and covering, cooling.Use powder
The mixture of accelerator and covering is crushed to a diameter of less than 100 microns of particle by broken machine.Then, by the proportioning of table 1, in
After 20 DEG C are well mixed above-mentioned accelerator and covering, epoxy resin, curing agent, epoxy-resin systems are obtained.
Tested viscosity change (50 DEG C, 1bar is placed 1 hour), hardening time (50 DEG C, 50bar), as a result it is listed in table 2.
The embodiment 1-8 of table 2 component and testing result
Embodiment 9-12
By the proportioning of table 3, with an agitator, after 90 DEG C are well mixed accelerator and covering, cooling.Use powder
The mixture of accelerator and covering is crushed to a diameter of less than 100 microns of particle by broken machine.Then, by the proportioning of table 1, in
After 25 DEG C are well mixed above-mentioned accelerator and covering, epoxy resin, curing agent, epoxy-resin systems are obtained.Only will wherein
Covering replace with covering shown in table 3.
Tested viscosity change (50 DEG C, 1bar is placed 1 hour), hardening time (50 DEG C, 50bar), as a result it is listed in table 3.
The embodiment 9-12 of table 3 component and testing result
Embodiment 13-15
By the raw material and proportioning of embodiment 11, with an agitator, in 100 DEG C by a portion accelerator (institute in table
State the accelerator of same covering mixing) and covering it is well mixed after, cool down.Using pulverizer by the mixed of accelerator and covering
Compound is crushed to a diameter of less than 100 microns of particle.
Then, by the proportioning of embodiment 11, in 30 DEG C by above-mentioned accelerator and covering hybrid particles, remaining promotion
After agent, epoxy resin, curing agent are well mixed, epoxy-resin systems are obtained.(50 DEG C, 1bar places 1 small for tested viscosity change
When), hardening time (50 DEG C, 1bar and 50bar), be as a result listed in table 4.
The embodiment 13-15 of table 4 component and testing result
Conclusion:A kind of epoxy-resin systems obtained by the present invention placed 1 hour under 50 DEG C, 1bar after viscosity B coefficent
Amount is respectively less than 150%;50 DEG C, the hardening time under 50bar be 10-30 seconds.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (9)
1. a kind of epoxy-resin systems, it is characterised in that including following component by weight:100 parts of epoxy resin, solidification
10-70 parts of agent, 1-20 parts of accelerator, 0.1-10 parts of covering.
2. a kind of epoxy-resin systems according to claim 1, it is characterised in that described curing agent is more comprising aliphatic
One kind in first amine curing agent.
3. a kind of epoxy-resin systems according to claim 1, it is characterised in that described accelerator is phenol or derivative
One kind in thing.
4. a kind of epoxy-resin systems according to claim 1, it is characterised in that described covering elects poly-succinic as
Glyceride or polyadipate glyceride.
5. a kind of epoxy-resin systems according to claim 1, it is characterised in that the covering is with disperse phase point
It is dispersed in asphalt mixtures modified by epoxy resin lipid phase, the average diameter of the covering dispersed phase is less than 100 microns.
6. a kind of epoxy-resin systems according to claim 1, it is characterised in that the covering is uncrosslinked, number is divided equally
Son amount is 5000-25000g/mol.
7. the preparation method of a kind of epoxy-resin systems according to claim 1, it is characterised in that method and step is as follows:
S1:After accelerator and covering are well mixed, cooling.S2:The mixture obtained by S1 is crushed to diameter using pulverizer
For the particle below 100 microns;S3:Particle made from S2 is mixed with epoxy resin and curing agent, epoxy-resin systems are produced.
8. a kind of preparation method of epoxy-resin systems according to claim 7, it is characterised in that the mixing temperature of the S1
Spend for 80-100 DEG C, the mixing temperature of the S3 is 20-30 DEG C.
9. a kind of epoxy-resin systems according to claim any one of 1-8 are applied to prepare fibre enhancement epoxy composite wood
Material.
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Citations (1)
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CN102295824A (en) * | 2011-07-08 | 2011-12-28 | 蓝星(北京)化工机械有限公司 | One-part high-performance epoxy resin composition for pultrusion |
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CN102295824A (en) * | 2011-07-08 | 2011-12-28 | 蓝星(北京)化工机械有限公司 | One-part high-performance epoxy resin composition for pultrusion |
Non-Patent Citations (2)
Title |
---|
ABDUL WAHAB ET AL.: "Development of poly(glycerol adipate) nanoparticles loaded with non-steroidal anti-inflammatory drugs", 《JOURNAL OF MICROENCAPSULATION》 * |
MICHAEL A. CARNAHAN ET AL.: "Synthesis and Characterization of Poly(glycerol-succinic acid) Dendrimers", 《MACROMOLECULES》 * |
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